CN1240689A - Process for preparing superfine powder by thermolyzing metal complex - Google Patents
Process for preparing superfine powder by thermolyzing metal complex Download PDFInfo
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- CN1240689A CN1240689A CN 98115767 CN98115767A CN1240689A CN 1240689 A CN1240689 A CN 1240689A CN 98115767 CN98115767 CN 98115767 CN 98115767 A CN98115767 A CN 98115767A CN 1240689 A CN1240689 A CN 1240689A
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Abstract
A process for preparing superfine powder by thermolyzing metal complex features that the complex of Ni, Co or Cu, which contains oximide or carboxyl is thermolyzed in nitrogen or other inertial gas to respectively obtain nm-class superfine powder of Ni, Co or Cu, or their oxides. Its advantages are no need of reducer and assistant, simple operation and high safety and purity. Said process can also be used to prepare supported Ni micropowder.
Description
The present invention relates to the thermal decomposition of metal complex, metal and oxide super fine preparation method thereof particularly relate to preparation method's technical field of nickel micro mist, cobalt or copper and oxide super fine thereof.
Ultrafine metallic micropowder has special physics, chemical property, has special using value at aspects such as catalyst, magnetic materials.According to " chemical industry progress " (1992, the fifth phase, p25) report, particle diameter can improve about ten times less than the nickel powder of 30nm than the selectivity of traditional Raney nickel; According to " chemical industry progress " (1993, the fourth phase, p21) report, the magnetic material that makes with nano level Fe, Co, Ni alloy can obtain the high letter/ratio of making an uproar; The ultra-fine Ni or the Al micro mist of adding 1% can make its combustion heat double in the solid fuel of rocket launching.Thereby the preparation method of research ultrafine metallic micropowder has crucial meaning.
The chemical preparation process of existing ultrafine metallic micropowder has: (1) high temperature gas phase reduction process, as U.S.'s " chemistry comment " (Chem.Rev.1982,82, p153-208), China " high chemical journal " (1994,15 (3)) wait report with H
2Or the method for CO reduction nickel hydroxide or nickel salt, but this method at high temperature uses fuel gas to have certain risk; (2) nickel salt solution reducing process, as China's " Acta PhySico-Chimica Sinica " (1996,12 (5), report p460-463), but in solution, carry out because of this method, and need add dispersant that the post processing of product is more loaded down with trivial details; (3) hydro-thermal hydrogenating reduction method, as China's " investigation of materials journal " (1995,6, report that p223-227) this method need be reacted in autoclave pressure, the while also exists product to need the trouble of solid, liquid separation.
The physical preparation method of existing ultrafine metallic micropowder has: (1) evaporation, see " Japanese applicating physical magazine " (Japanese Journal of Applied Physics, 1977,16 (5) p705-717); (2) laser method, see " Chinese laser " (1989,16 (12), p741-742).These preparation methods require harsh to equipment, be difficult to realize industrial production.
The present invention proposes a kind ofly to decompose the method prepare super fine with the metal complex direct heat, to overcome the above-mentioned defective of prior art.
The present invention prepares the method for super fine with the metal complex thermal decomposition, is characterised in that with the metal complex that contains oximido or carboxyl be raw material, adds thermal decomposition under nitrogen or other inert atmosphere, can obtain nano level metal and/or its oxide super fine; Described metal complex comprises the oximido or the carboxyl complex of nickel, cobalt or copper, and the part of described complex comprises α-oximido carboxylic acid, dimethylglyoxime, formaldoxime.
When described metal complex is the oximido or the carboxyl complex of nickel, when part comprises α-oximido carboxylic acid, dimethylglyoxime, formaldoxime, can obtain nano level metal nickel micro mist.
Add thermal decomposition as if above-mentioned nickel complex is dispersed on the inorganic porous carrier, then can obtain the load-type nickel micro mist; Described inorganic porous carrier comprises silica, aluminium oxide, zeolite or diatomite.
When described metal complex is cobalt complex, then can obtain the mixture of metallic cobalt and cobalt oxide, they are nano-scale particle;
When described metal complex is copper complex, then can obtain the mixture of metallic copper and cuprous oxide, they also are nano-scale particle.
Compared with prior art, the inventive method has following advantage:
Because the inventive method adopts metal complex as raw material, need not to add in addition reducing agent, and need not to make used additives, thereby avoided existing high temperature gas phase reduction process to use H down by high temperature
2Or the danger of fuel gas such as CO, easy to operate, safety; Organic ligand can decompose fully in the present invention's reaction, thereby product is pure; The inventive method adopts solid phase to decompose, and directly obtains product, easy operating, the trouble of having avoided liquid phase reduction to need solid, liquid to separate.
Below be the embodiment of the inventive method:
Embodiment 1: the nickel nitrate solution of 0.1M is added in α-oximido propionic acid (PAO) solution of 0.1M of equivalent, obtain the precipitation of Ni-PAO complex after the stirring; With sedimentation and filtration, washing, oven dry; Under nitrogen protection, be heated to 310 ℃ and kept 10 minutes, obtain black powder.(XRD) turns out to be metallic nickel through the powder X-ray diffraction, and Electronic Speculum detects and shows that the nickel powder dispersion is more even, and particle diameter is 5-15nm.
Embodiment 2: the nickel nitrate solution of 0.1M is added in the ethanolic solution of dimethylglyoxime of 0.1M of equivalent and stir, make Ni dimethylglyoxime complex precipitation; With sedimentation and filtration, washing, oven dry; Under nitrogen protection, be heated to 350 ℃ and kept 30 minutes, obtain black powder.Turn out to be metallic nickel through the powder X-ray diffraction, Electronic Speculum detects and shows that the nickel powder dispersion is more even, and particle diameter is 5-20nm.
Embodiment 3: dimethylglyoxime nickel complex 2 grams that embodiment 2 methods are made are dissolved in chloroform, add 10 gram 10-40 μ m silica.Obtain containing the silica of dimethylglyoxime after stirring under the room temperature, evaporating; under nitrogen protection, be heated to 400 ℃; and kept 30 minutes; obtain black powder; XRD alleged occurrence metallic nickel and silica; Electronic Speculum detects and shows on the surface of nano level fine particle attached to micron particles, forms the load-type nickel micro mist.
Embodiment 4: cobalt nitrate solution is added in the PAO solution, stir, make the Co-PAO complex.Under nitrogen protection, be heated to 500 ℃ and kept 30 minutes, promptly obtain black powder.XRD turns out to be the mixture of metallic cobalt, cobalt oxide, cobalt protoxide, calculates from the peak width of XRD, and various powder are nano-scale particle, and average grain diameter is about 20-25nm.
Embodiment 5: Schweinfurt green solution is added in the PAO solution, stir, make the Cu-PAO complex.Under nitrogen protection, be heated to 280 ℃ and kept 30 minutes, promptly obtain black powder.XRD turns out to be the mixture of metallic copper, cuprous oxide, calculates from the peak width of XRD, and the average grain diameter of cuprous oxide powder is about 10nm.
Claims (2)
1, a kind ofly prepares the method for super fine, be characterised in that with the metal complex that contains oximido or carboxyl be raw material, under nitrogen or other inert atmosphere, add thermal decomposition with the metal complex thermal decomposition; Described metal complex comprises the oximido or the carboxyl complex of nickel, cobalt or copper, and the part of described complex comprises α-oximido carboxylic acid, dimethylglyoxime, formaldoxime.
2, the method for preparing super fine according to claim 1 with the metal complex thermal decomposition is characterised in that described nickel complex is dispersed on the inorganic porous carrier, then can obtain the load-type nickel micro mist; Described inorganic porous carrier comprises silica, aluminium oxide, zeolite or diatomite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98115767 CN1103257C (en) | 1998-07-08 | 1998-07-08 | Process for preparing superfine powder by thermolyzing metal complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98115767 CN1103257C (en) | 1998-07-08 | 1998-07-08 | Process for preparing superfine powder by thermolyzing metal complex |
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| Publication Number | Publication Date |
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| CN1240689A true CN1240689A (en) | 2000-01-12 |
| CN1103257C CN1103257C (en) | 2003-03-19 |
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| CN 98115767 Expired - Fee Related CN1103257C (en) | 1998-07-08 | 1998-07-08 | Process for preparing superfine powder by thermolyzing metal complex |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302884C (en) * | 2004-12-02 | 2007-03-07 | 黄德欢 | Method and apparatus for preparing mixed powder of nano gold and sodium chloride |
| CN1302850C (en) * | 2004-12-02 | 2007-03-07 | 黄德欢 | Method for preparing supported nano gold powder by thermal decomposition and apparatus therefor |
| CN1302849C (en) * | 2004-12-02 | 2007-03-07 | 黄德欢 | Method for preparing supported nano gold powder |
| CN100337752C (en) * | 2006-02-14 | 2007-09-19 | 钢铁研究总院 | Gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst |
| US7777059B2 (en) | 2003-12-18 | 2010-08-17 | Basf Se | Copper(I) formate complexes |
| CN101966418A (en) * | 2010-08-23 | 2011-02-09 | 上海电力学院 | Absorption solution for NO in coal-fired flue gas and preparation method and application thereof |
| CN101784352B (en) * | 2007-07-26 | 2011-11-02 | Lg化学株式会社 | Preparation method of copper particle composition |
| CN102350505A (en) * | 2011-09-22 | 2012-02-15 | 浙江师范大学 | Preparation method for nickel/graphene nanometer compound material |
| CN105152969A (en) * | 2015-08-19 | 2015-12-16 | 西安近代化学研究所 | Dimethylglyoxime magnesium and preparation method thereof |
| CN108526490A (en) * | 2018-05-14 | 2018-09-14 | 六盘水中联工贸实业有限公司 | A method of producing copper powder with copper chloride or stannous chloride |
| CN109994741A (en) * | 2019-04-12 | 2019-07-09 | 济南大学 | A kind of carbon coating transition metal atoms cluster oxygen reduction catalyst and preparation method and purposes |
-
1998
- 1998-07-08 CN CN 98115767 patent/CN1103257C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7777059B2 (en) | 2003-12-18 | 2010-08-17 | Basf Se | Copper(I) formate complexes |
| CN1302884C (en) * | 2004-12-02 | 2007-03-07 | 黄德欢 | Method and apparatus for preparing mixed powder of nano gold and sodium chloride |
| CN1302850C (en) * | 2004-12-02 | 2007-03-07 | 黄德欢 | Method for preparing supported nano gold powder by thermal decomposition and apparatus therefor |
| CN1302849C (en) * | 2004-12-02 | 2007-03-07 | 黄德欢 | Method for preparing supported nano gold powder |
| CN100337752C (en) * | 2006-02-14 | 2007-09-19 | 钢铁研究总院 | Gas phase permeation precipitation method for preparation of supported nanometer nickel hydrogenation catalyst |
| CN101784352B (en) * | 2007-07-26 | 2011-11-02 | Lg化学株式会社 | Preparation method of copper particle composition |
| CN101966418A (en) * | 2010-08-23 | 2011-02-09 | 上海电力学院 | Absorption solution for NO in coal-fired flue gas and preparation method and application thereof |
| CN102350505A (en) * | 2011-09-22 | 2012-02-15 | 浙江师范大学 | Preparation method for nickel/graphene nanometer compound material |
| CN105152969A (en) * | 2015-08-19 | 2015-12-16 | 西安近代化学研究所 | Dimethylglyoxime magnesium and preparation method thereof |
| CN108526490A (en) * | 2018-05-14 | 2018-09-14 | 六盘水中联工贸实业有限公司 | A method of producing copper powder with copper chloride or stannous chloride |
| CN109994741A (en) * | 2019-04-12 | 2019-07-09 | 济南大学 | A kind of carbon coating transition metal atoms cluster oxygen reduction catalyst and preparation method and purposes |
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| Publication number | Publication date |
|---|---|
| CN1103257C (en) | 2003-03-19 |
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